EP0554276A4 - - Google Patents

Info

Publication number
EP0554276A4
EP0554276A4 EP91917559A EP91917559A EP0554276A4 EP 0554276 A4 EP0554276 A4 EP 0554276A4 EP 91917559 A EP91917559 A EP 91917559A EP 91917559 A EP91917559 A EP 91917559A EP 0554276 A4 EP0554276 A4 EP 0554276A4
Authority
EP
European Patent Office
Prior art keywords
polyacetylene
monomer
imageable
polymer
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91917559A
Other languages
English (en)
Other versions
EP0554276B1 (en
EP0554276A1 (en
Inventor
David F Lewis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ISP Investments LLC
Original Assignee
ISP Investments LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Publication of EP0554276A1 publication Critical patent/EP0554276A1/en
Publication of EP0554276A4 publication Critical patent/EP0554276A4/en
Application granted granted Critical
Publication of EP0554276B1 publication Critical patent/EP0554276B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
    • G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/025—Non-macromolecular photopolymerisable compounds having carbon-to-carbon triple bonds, e.g. acetylenic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/146—Laser beam
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition

Definitions

  • thermochromic recording medium having a thermal sensitivity above about 50°C, preferably above about 80°C, which comprises an imageable crystalline polyacetylene monomer in contact with imageable polyacetylene polymer particles of the same or different polyacetylene species wherein the mole ratio of said monomer to said polymer is between about 1:1 and about 1000:1, preferably between about 10:1 and about 500:1.
  • the imageable medium is generally prepared by forming separate dispersions of the polyacetylene monomer and the polyacetylene polymer in a binder and then either adding and mixing the polymer dispersion with the monomer dispersion or forming a separate contiguous film of the polymer dispersion on a surface of the monomer dispersion.
  • the polyacetylene polymer can be applied as a separate layer over or below the monomer layer as a thin film e.g. by the Lang uir-Blodgett deposition technique, by spin coating, spray coating or the like or as a dispersed layer wherein the polymer particles are fixed in a binder.
  • the imageable medium may also contain an energy absorbing, heat transferring agent having an optical absorption in a wavelength similar to the wavelength of the image transmitting device and, in cases where infrared transmission in the 650 to 1,500 nm wavelength range is desired the incorporation of such an energy absorbing, heat transferring agent is recommended.
  • said agent is added to at least one of the imageable polyacetylene components in a concentration sufficient to provide a peak optical density of between about 0.1 and about 3, preferably between about 0.2 and about 2.
  • the polyacetylene monomer is supported on a suitable substrate such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, nylon, polyethylene terephthalate, glass, paper, cellophane, cellulose nitrate, cellulose acetate, polystyrene, teflon, polychlorotrifluoroethylene, polycarbonate, glass, ceramic, metal, wood and the like; however, transparent substrates supporting polyacetylene monomer microcrystals dispersed in a binder are preferred.
  • the dispersed monomer forms a layer on the substrate having a thickness of from about 0.1 to about 5 urn and said dispersed polymer particles forms a layer over the monomer layer having a thickness of from about 0.02 to about 1 urn which is sufficient to provide a desired peak optical density of between about 0.1 and about 3, preferably between about 0.2 and 2.
  • the dispersed polymer can be disposed below the monomer as a separate layer between the monomer and the support.
  • the polyacetylene monomers of this invention include any of the known crystalline polyacetylenes which are capable of thermochromic changes, for example, those disclosed in U.S. patents 3,501,303; 4,215,208 and 4,784,934, incorporated herein by reference. Of this group 0.02 um to 1 urn microcrystals of the diacetylene monomers containing carboxyl, urea, urethane, ether and carbamate substitution are preferred.
  • suitable polyacetylenic monomers include 1,6-diamino-l,6-hexadiyne , 2,4-hexadiyn-l,6-bis(n-butyl carbamate) , 2 ,4-hexadiyn-l,6-bis(cyclohexyl urea) , 1,12-(3,10-dioxa-5,7-dodecadiyndiyl) dibenzoate, 2,5-octadiyn-l,8-bis(n-propyl carbamate) , 3,5-octadiyn-l,8-bis(n-propyl carbamate) , 5,7-dodecadiyn-l,12-bis(isopropyl carbamate) , 5,7-dodecadiyn-l,12-bis(n-butyl carbamate) , 2,4-hexadiyn-l
  • the imageable polyacetylene polymers of this invention are thermochromic homopolymers derived from one of the above polyacetylene monomers by exposure to short wavelength radiation. Preferred of this group are the thermochromic polyacetylene homopolymers of diacetylenes.
  • the poly(diacetylene) contains repeating units of
  • R and R' are as defined above.
  • the polyacetylene polymer employed in the imageable medium can be a homopolymer of the same species as the monomer or a homopolymer derived from a different species within the scope of polyacetylene monomers defined above.
  • the polyacetylene homopolymers of this invention are readily prepared from a corresponding monomer by exposure to ionizing radiation from a source of energy such as UV light. X-ray, gamma-ray, electron beam, etc. It is to be understood that mixtures of polyacetylene monomer and mixtures of the polyacetylene polymer can also be employed as the imageable medium of this invention.
  • the energy absorbing heat transferring agents of the present invention are dyes having a wide absorption range and include polycarbocyanine dyes, squarylium dyes and others including energy absorbing metal complex dyes such as for example diimine iron complex, dithiol nickel complex, the dyes of indigo, anthraquinone, azulenium, indolizinium, naphthalocyanine, naphthoquinone and its analogs, phthalocyanine, polymethine, pyrylium, thiapyrylium, telluropyrylium, triaryl ammonium, triquinocycloalkane, and any of the specific dyes disclosed in the Journal of Imaging Science, Volume 32, number 2, March/April 1988, pages 51-56 (ORGANIC ACTIVE LAYER MATERIALS FOR OPTICAL RECORDING by James E.
  • metal complex dyes such as for example diimine iron complex, dithiol nickel complex, the dyes of indigo, anthraquino
  • Dispersions of the imageable medium are prepared under atmospheric conditions by forming an emulsion, suspension or dispersion, preferably an aqueous dispersion containing a binder with from about 0.02 um to about 5 urn diameter crystals, preferably from 0.1 um to 1.0 um diameter crystals of the polyacetylene monomer and with polyacetylene polymer particles of 0.1 to 1.0 diameter to provide substrate coating layers containing from about 1 to about 90 wt. %, preferably from about 25 to about 75 wt. % polyacetylene solids in the dried coating.
  • binder materials are natural and synthetic plastics, resins, waxes, colloids, gels and the like including gelatins, desirably photographic-grade gelatin, various polysa ⁇ charides including dextran, dextrin, hydrophilic cellulose ethers and esters acetylated starches, natural and synthetic waxes including paraffin, beeswax, polyvinyl-lactams, polymers of acrylic-and methacrylic esters and amides, hydrolyzed interpolymers of vinyl acetate and unsaturated addition polymerizable compounds such as maleic anhydride, acrylic and methylacrylic esters and styrene, vinyl acetate polymers and copolymers and their derivatives including completely and partially hydrolyzed products thereof, polyvinyl acetate, polyvinyl alcohol, polyethylene oxide polymers, polyvinylpyrrolidone polyvinyl acetals including polyvinyl acetaldehyde acetal, polyvinyl but
  • binders that can be applied from an aqueous medium, as a dispersion, emulsion or solution and particularly preferable are water soluble binder materials.
  • water soluble binder materials As is well known in the art in the preparation of smooth uniform continuous coatings of binder materials, there may be employed therewith small amounts of conventional coating aids as viscosity controlling agents, surface active agents, leveling agents dispersing agents and the like.
  • Binder solutions in the absence of any polyacetylene component, can also be applied as a separate surface coating on the recording film to provide protection against abrasion, moisture, etc.
  • the present energy absorbing, heat transferring dye can be incorporated in the imaging medium by various procedures.
  • the dye can be added to one or both of the polyacetylene dispersions, it can be added to the mixed dispersion of monomer and polymer it can be added to a non-dispersed polymer monolayer or it can form a separate layer of the imageable recording medium.
  • the dye is employed in an amount sufficient to provide a peak optical density of between about 0.1 and about 3, preferably between about 0.2 and about 2.
  • the dye in cases where the dye is not water soluble and aqueous dispersions of the monomer and polymer are involved, the dye can be dissolved in a suitable inert solvent such as a ketone, benzene, alcohol, and the like for addition to the monomer and/or polymer dispersion.
  • a suitable inert solvent such as a ketone, benzene, alcohol, and the like
  • the weight ratio of polyacetylene monomer to dye in the resulting imageable medium can vary in an extremely wide range, e.g. from about 10,000:1 to about 1:10 depending on the components involved.
  • the monomer/polymer dispersion is applied to the substrate and dried thereon to provide a recording film wherein the monomer and polymer particles are fixed.
  • the monomer can be applied separately to the substrate and the polymer layer can be subsequently deposited as a separate surface layer before or after drying of the monomer layer.
  • Another alternative involves initially coating the substrate with the polymer and subsequently coating the polymer with the monomer layer. The monomer layer is then optionally coated with a final polyacetylene polymer layer of the same or different species as the monomer subsurface.
  • the polymer and/or monomer can also be applied as one or more mono-molecular layers as formed by the Langmuir-Blodgett technique, spin or spray coating methods.
  • the dried imageable medium is then exposed to light emanations which impinge and generate heat on the film surface in areas of a predetermined design consistent with a desired pattern to create a color change in the colored polyacetylene polymer portion; and a corresponding latent image in the polyacetylene monomer portion of the medium.
  • a dye of the above described group having an optical absorbance in the wavelength transmission of the imaging device is incorporated therein so as to generate the heat necessary to activate the polymer and to deactivate the monomer in the exposed areas, i.e. presumably, to cause the original crystalline phase of the monomer to become an amorphous phase.
  • the imaged medium is then subjected to an overall exposure -of short-wave radiation generated from a source such as UV light, electron beam, gamma-ray.
  • a source such as UV light, electron beam, gamma-ray.
  • X-ray, beta-ray, neutrons, alpha-particles and the like to convert the unexposed area of the monomer portion to a color or color intensity which is readily distinguishable from the color of the portion to which the image is transmitted.
  • thermochromic change dramatically altering the absorption of blue light (e.g. a blue to yellow thermochromic change) since this change will provide the highest contrast for duplication to other recording photosensitive recording media, particularly those containing photopolymers, sensitive to blue and ultraviolet light as are commonly employed in commercial photolithographic printing plates and etch resists used in the preparation of printed board circuits.
  • polyacetylenes which are converted to other hues or hue intensities in the red, magenta, green, brown, blue and other color spectra all provide good image definition.
  • the types of laser which are suitably employed with the present composition include compact semi-conductor, solid state, gas, metal-vapor, UV, and dye lasers.
  • semi-conductor diode lasers or solid state lasers are preferred and semi-conductor diode lasers are most preferred.
  • Similar light sources such as a zenon arc lamp, a mercury arc lamp, a tungsten-quartz halogen lamp and the like, can be substituted for laser imaging devices in the present invention.
  • the techniques of short wavelength exposure to develop the latent image are well known, thus further amplification is not required.
  • a detector can be deployed. Suitable types include thermopile, colorimeter, and pyroelectric detectors which have a spectral response between about 200 and 5,000 nm and a power rating of from 7 x 10 ""9 to 200 watts.
  • Pentacosa-10,12-diynoic acid (50 g.) is dissolved in 150 g. of ethyl acetate at 50°C. and filtered to provide Solution A.
  • Solution B is prepared by dissolving 50 g. of photographic gelatin and 2 p of Alkanol XC ⁇ 1) in 900 ml of deionized water at 50°C.
  • Dispersion A While stirring Solution B at 50°C. in a high intensity mixer. Solution A is added over a 2 minute period, after which agitation is maintained for an additional 2 minutes. The resulting emulsion is then chill set at 4°C. and vacuum dried to about 20% weight loss to remove the ethyl acetate. The dispersion thus formed is melted and reconstituted to form Dispersion A by adding distilled water to replace the liquid lost during vacuum drying.
  • Dispersion B is made in a similar way to Dispersion A of Example 1 except that 2,4-hexadiyn-l,6-bisethylcarbamate replaces the pentacosa-10,12-diynoic acid.
  • Dispersion C is made by exposing a portion of Dispersion A to 10 MRad of Co 60 radiation, so as to develop a deep blue color.
  • Dispersion A Another portion of Dispersion A (5 g.) with 0.1 ml of a coating aid ⁇ 2 ) is melted at 40°C. and coated on 4 mil polyester film base to yield a dry coating approximately 2.5 um thick (designated as Coating A).
  • Coating A a dry coating approximately 2.5 um thick
  • the pentacosa-10,12-diynoic acid is polymerized to provide a deep blue colored coating, designated as Coating B.
  • Coatings C and D were prepared in a manner similar to Coatings A and B respectively except that 0.1 gm of dye IR-125 ⁇ 1 ⁇ was added to Dispersion A prior to the coating operation.
  • Dispersion C was melted, a small portion of coating aid was added and the resulting material coated to provide a dry layer of 0.25 um thickness over Coating A. This product was designated as Coating E.
  • Coatings F, G and H were prepared from coatings B, C and D respectivel .
  • Dispersion A (25 g.) was mixed with 2 gm of dispersion C and a small portion of coating aid was added together with 0.25 g. of dye IR-125 before coating a 2 um (dry thickness) layer on 4 mil polyester film base, to provide Coating I.
  • Dispersion B was coated on a 4 mil polyester base to yield a dry thickness of about 1 u , following which the coating was exposed to ultraviolet radiation at 254 nm sufficient to turn the coating a deep orange-yellow with an optical density of about 2.0. This sample was then over-coated with Dispersion A to an additional dry thickness of 5 um and the product designated as Coating J.
  • Coating K is prepared in a similar manner to Coating J of Example 8, except that prior to overcoating, IR-125 dye was added to Dispersion A in the proportion 0.1 gm of IR-125 per 100 g. of Dispersion A.
  • Dispersion B 25 g.
  • 0.25 gm of Dispersion C 0.25 gm of Dispersion C were mixed, melted at 40°C. and 0.2 g. of IR-125 dye was added and dissolved therein. After addition of a small amount of coating aid the mixed dispersion was coated on 4 mil polyester base to yield a coated layer with a dry thickness of 4.0 um and the product designated as Coating
  • Coatings A to L were exposed to the 830 nm wavelength radiation from a 5 mW GaAlAs laser, focused to a spot size of about 1 um. The beam was scanned across the surface of the samples at a rate of 300 cm/sec, after which the coatings were examined under a microscope and the following observations recorded.
  • Example 11 The procedure of Example 11 was repeated except that a 5 mW Ar ion laser was employed with an emanation at 514 nm wavelength. The following results were noted when the samples were inspected under a microscope.
  • thermochromic polyacetylene polymer capable of absorbing the laser radiation.
  • the presence of the infrared absorbing dye is of no consequence since it does not absorb the radiation from the Ar ion laser.
  • Coatings J and K produce no markings in this experiment because the yellow polyacetylene polymer contained in them, does not absorb radiation at 514 nm.
  • Example 11 The coated samples from Example 11 were further exposed to ultraviolet radiation at 254 nm with the following findings.
  • This example shows that when the infrared absorbing dye is present to absorb the laser radiation, it creates a latent image by deactivating the unpolymerized polyacetylene, and this image is revealed by the exposure to UV radiation and subsequent polymerization of the polyacetylene in the non-imaged areas.
  • the original low contrast lines formed by infrared exposure of the Samples. of Coatings G, I, K and L from Example 11 are then transformed into high contrast lines by the subsequent UV exposure.
  • the original appearance of these low contrast lines form instantaneously after infrared exposure and can be detected by suitable photodetection means and provide a predictor of the ultimate formation of a high contrast image after application of an overall exposure to UV or other low wavelength radiation.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP91917559A 1990-10-23 1991-09-16 Imageable recording films Expired - Lifetime EP0554276B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US601546 1990-10-23
US07/601,546 US5139928A (en) 1990-10-23 1990-10-23 Imageable recording films
PCT/US1991/006631 WO1992007298A1 (en) 1990-10-23 1991-09-16 Imageable recording films

Publications (3)

Publication Number Publication Date
EP0554276A1 EP0554276A1 (en) 1993-08-11
EP0554276A4 true EP0554276A4 (enExample) 1995-08-02
EP0554276B1 EP0554276B1 (en) 1997-09-17

Family

ID=24407908

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91917559A Expired - Lifetime EP0554276B1 (en) 1990-10-23 1991-09-16 Imageable recording films

Country Status (5)

Country Link
US (1) US5139928A (enExample)
EP (1) EP0554276B1 (enExample)
CA (1) CA2093115C (enExample)
DE (1) DE69127702T2 (enExample)
WO (1) WO1992007298A1 (enExample)

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US5731112A (en) * 1996-05-23 1998-03-24 Isp Investments Inc. Processless diacetylenic salt films capable of developing a black image
US9086489B2 (en) 2003-02-27 2015-07-21 Jp Laboratories, Inc Personal and area self-indicating instant radiation alert dosimeter
US8115182B1 (en) 2003-02-27 2012-02-14 Gordhanbhai N Patel Personal and area self-indicating radiation alert dosimeter
JP4852410B2 (ja) * 2003-02-27 2012-01-11 ジェイピー ラボラトリーズ インコーポレイテッド 放射線モニタリング装置およびその製造方法
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GB0801440D0 (en) * 2008-01-25 2008-03-05 Datalase Ltd Polychromic substances and their use
EA019299B9 (ru) * 2008-07-03 2014-05-30 Дейталейз Лтд. Полихромные вещества и их применение
CN102144064B (zh) * 2008-09-03 2014-09-17 数据激光有限公司 激光成像纸
EP2332012B1 (en) * 2008-09-10 2014-07-09 DataLase Ltd Energy activated compositions
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Also Published As

Publication number Publication date
DE69127702D1 (de) 1997-10-23
DE69127702T2 (de) 1998-03-05
CA2093115C (en) 2002-10-29
EP0554276B1 (en) 1997-09-17
WO1992007298A1 (en) 1992-04-30
EP0554276A1 (en) 1993-08-11
CA2093115A1 (en) 1992-04-24
US5139928A (en) 1992-08-18

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